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United States Patent |
6,187,937
|
Fields, Jr.
,   et al.
|
February 13, 2001
|
Preparation of N-phenyl-benzoquinoneimine from hydroxydiphenylamines
Abstract
A hydroxydiphenylamine compound can be converted to an N-phenylquinoneimine
by reacting the hydroxydiphenylamine with oxygen or an oxygen containing
gas in the presence of a modified activated carbon catalyst, the catalyst
having had surface oxides removed therefrom.
Inventors:
|
Fields, Jr.; Donald L. (Copley, OH);
Stern; Michael K. (Clayton, MO);
Lodaya; Jayant Shivji (Akron, OH)
|
Assignee:
|
Flexsys America L.P. (Akron, OH)
|
Appl. No.:
|
264989 |
Filed:
|
December 23, 1998 |
Current U.S. Class: |
552/302; 552/301 |
Intern'l Class: |
C07C 050/04 |
Field of Search: |
552/301,302
|
References Cited
U.S. Patent Documents
4158643 | Jun., 1979 | Sinha | 252/447.
|
4264776 | Apr., 1981 | Hershman et al. | 564/384.
|
4624937 | Nov., 1986 | Chou | 502/180.
|
4968843 | Nov., 1990 | Cottman | 564/397.
|
5053540 | Oct., 1991 | Cottman | 564/397.
|
5068439 | Nov., 1991 | Cottman | 564/434.
|
5189218 | Feb., 1993 | Desmurs et al. | 564/272.
|
5371289 | Dec., 1994 | Cottman et al. | 564/396.
|
Foreign Patent Documents |
448 899A1 | Oct., 1991 | EP | .
|
617 004A1 | Sep., 1994 | EP | .
|
Other References
Chem. Abstract 87:133491, Ram, Nathu et al., Automation of
p-hydroxydiphenylamine, Tetrahedron, 33 (8), 887-90, 1977 (Abstract only).
|
Primary Examiner: Qazi; Sabiha N
Attorney, Agent or Firm: Morris; Louis A.
Parent Case Text
This application claims the benefit of U.S. Provisional Application No.
60/071,690, filed Jan. 16, 1998.
Claims
What is claimed is:
1. A process for preparing an N-phenylquinone-imine (NPQI) comprising
oxidizing a corresponding hydroxydiphenylamine (HDA) in the presence of
oxygen or an oxygen containing gas and a modified activated carbon
catalyst, with said catalyst having been modified by having surface oxides
removed therefrom.
2. The process of claim 1 wherein the hydroxydiphenylamine (HDA) is
4-hydroxydiphenylamine.
3. The process of claim 1 wherein the HDA is initially dissolved and/or
mixed in a solvent.
4. The process of claim 3 wherein the solvent is an alcohol, ketone,
aromatic/aliphatic hydrocarbon, nitrile, halogenated solvents,
N-methylpyrrolidone, THF, ethylacetate, dimethylformamide,
dimethylsulfoxide, water, or mixtures thereof.
5. The process of claim 4 wherein the alcohol solvent is selected from
methanol, ethanol, isopropanol, methyl isobutyl carbinol and ethylene
glycol.
6. The process of claim 1 wherein the reaction takes place at a temperature
of from about 0.degree. C. to about 100.degree. C.
7. The process of claim 1 wherein a tertiary amine is further added to the
reaction.
8. The process of claim 7 wherein the tertiary amine is triethylamine.
9. The process of claim 1 wherein the oxides are removed from the modified
activated carbon catalyst surface by subjecting activated carbon to an
oxidizing agent and then pyrolizing the activated carbon in an oxygen free
atmosphere at a temperature in the range of about 500.degree. C. to about
1500.degree. C.
10. The process of claim 1 wherein the oxides are removed from the
activated carbon catalyst surface by simultaneously pyrolizing the
activated carbon in the presence of NH.sub.3 and an oxygen containing gas
that reacts with the oxides on the surface of the activated carbon at
pyrolizing temperatures of about 500.degree. C. to about 1500.degree. C.
11. A process for production of an N-phenylquinone-imine comprising:
(a) providing a hydroxydiphenylamine in a solvent system;
(b) oxidizing said hydroxydiphenylamine in the presence of oxygen or an
oxygen containing gas and a modified activated carbon catalyst to form an
N-phenylquinone-imine;
(c) filtering the modified activated carbon catalyst from the resulting
product of step (b); and
(d) isolating the N-phenylquinone-imine from the resulting product of step
(c);
wherein said modified activated carbon catalyst is characterized by having
had surface oxides removed therefrom.
12. The process of claim 11 wherein the solvent is an alcohol, ketone,
aromatic/aliphatic hydrocarbon, nitrile, halogenated solvents,
N-methylpyrrolidone, THF, ethylacetate, dimethylformamide,
dimethylsulfoxide, water, or mixtures thereof.
13. The process of claim 12 wherein the solvent is selected from methanol,
ethanol, isopropanol, methyl isobutyl carbinol, ethylene glycol, toluene,
xylenes, acetone, and methyl isobutyl ketone, or mixtures thereof.
14. The process of claim 11 wherein the reaction takes place at a
temperature of from above 0.degree. C. to about 150.degree. C.
15. The process of claim 11 wherein the reaction takes place at a
temperature of from about 15.degree. to about 75.degree. C.
16. The process of claim 11 wherein the pressure of the oxygen in the
reaction is from atmospheric to about 1000 psig O.sub.2.
17. The process of claim 11 wherein the pressure of the oxygen in the
reaction is from about 20 psig to about 500 psig O.sub.2.
18. The process of claim 11 wherein a tertiary amine is further added to
the reaction.
19. The process of claim 18 wherein the tertiary amine is triethylamine.
20. The process of claim 11 wherein the oxides are removed from the
modified activated carbon catalyst surface by subjecting activated carbon
to an oxidating agent and then pyrolizing the activated carbon in an
oxygen free atmosphere at a temperature in the range of about 500.degree.
to about 1500.degree. C.
21. The process of claim 11 wherein the oxides are removed from the
activated carbon catalyst surface by simultaneously pyrolizing the
activated carbon in the presence of NH.sub.3 and an oxygen containing gas
that reacts with the oxides on the surface of the activated carbon at
pyrolizing temperatures of about 500.degree. C. to about 1500.degree. C.
Description
FIELD OF THE INVENTION
This invention relates to a novel process for the preparation of
N-phenyl-benzoquinoneimines from their corresponding hydroxydiphenylamines
using an activated carbon catalyst which has had surface oxides removed
therefrom.
BACKGROUND OF THE INVENTION
The class of cyclic enones is well known in organic chemistry. Best known
examples of cyclic-enones are quinones such as, for example, the
benzoquinones, naphthoquinones, anthraquinones, phenanthraquinones, and
the like. 1,4-Benzoquinone is commonly referred to as quinone. Quinones
are generally brightly colored compounds and have versatile applications
in chemical synthesis, biological uses, as redox materials, as well as in
industry. There are several review articles on the chemistry and
applications of quinones including, for example, Kirk-Othmer Encyclopedia
of Chemical Technology, Third ed., Vol. 19, pages 572-605, John Wiley &
Sons, New York, 1982.
The synthesis of quinones is well documented. See, for example, J. Cason,
Synthesis of Benzoquinones by Oxidation, in Organic Synthesis, Vol. IV,
page 305, John Wiley & Sons, New York (1948). Quinones generally are
prepared by oxidizing the appropriately disubstituted aromatic hydrocarbon
derivatives, the substituents being hydroxyl or amino groups in the ortho
or para positions. 1,4-Benzoquinone, for example, can be made from the
oxidation of hydroquinone, p-aminophenol or p-phenylenediamine, or
sometimes from quinic acid. The reagents generally used for the oxidation
are dichromate/sulfuric acid mixture, ferric chloride, silver (II) oxide
or ceric ammonium nitrate. Such methods are generally performed in
solvents which may need elaborate waste disposal procedures. Some
processes may also take several hours for completion of the reaction.
Thus, some of the prior art processes utilize a catalytic agent to achieve
an acceptable reaction rate while other processes proceed without
catalysts. The process according to the present invention utilizes an
oxidation mechanism which provides extremely high conversion, high
selectivity, and fast reaction rates.
A prior art process which utilizes a catalyst in the preparation of an
N-phenylquinone-imine compound is disclosed by Desmurs, et al. in U.S.
Pat. No. 5,189,218. The process of Desmurs, et al., which converts a
N-(4-hydroxyphenyl) aniline into N-phenylbenzoquinone-imine, utilizes a
manganese, copper, cobalt, and/or nickel compound as a catalyst in an
oxidation type reaction.
Other processes which convert hydroxydiphenylamines to
N-phenylquinone-imines via stoichiometric oxidation using potassium or
sodium dichromate catalysts are disclosed by Cottman in U.S. Pat. No.
4,968,843, U.S. Pat. No. 5,068,439, U.S. Pat. No. 5,053,540, U.S. Pat. No.
5,371,289,
EP 448,899 and EP 617,004.
Denisov, et al. (Bull. Acad. Sci. USSR Div. Chem. Sci., 37 (10), 1988)
disclose preparation of N-phenylquinone-imine by reacting 4-anilino-phenol
(4-hydroxydiphenylamine) with an MnO2 catalyst in a benzene solvent
system.
Ram et al. (Tetrahedron, 33(8), 887-90, 1977) teach a non-catalytic
autoxidation reaction process for conversion of p-hydroxydiphenylamine to
N-phenyl-p-benzoquinone-imine.
The above process of Desmurs, et al., which uses a metal catalytic
component, along with any other processes which utilize a metal catalyst,
have several drawbacks. Not only are the metal catalysts relatively
expensive, they raise important environmental concerns. For example,
effluent streams and products can be contaminated by such metals. Further,
recovery of the catalyst for reuse can be prohibitively expensive.
Various non-heavy metal catalysts are known in the art. For example,
activated carbon catalysts, which are typically prepared by heating carbon
to high temperatures (800.degree. C. to 900.degree. C.) with steam or with
carbon dioxide to bring about a porous particulate structure and increased
surface area, are well known oxidation catalysts. U.S. Pat. No. 4,264,776,
for example, discloses and claims a process for preparing secondary amines
by catalytic oxidation of tertiary amines using an activated carbon
catalyst.
U.S. Pat. No. 4,158,643 teaches a method for oxidation modification of an
activated carbon support in which oxygen is added to the surface of the
activated carbon, and then the carbon support is impregnated with an inert
hydrophobic compound. The carbon support, which may be any commercially
available activated carbon for vapor phase activation use, is useful in
oxidizing carbon monoxide in the presence of sulfur dioxide for an
extended period of time.
U.S. Pat. No. 4,624,937 provides a method for preparing activated carbon
for catalytically oxidizing tertiary amines or secondary amines in the
presence of oxygen or an oxygen-containing gas to selectively produce
secondary or primary amines. The method of U.S. Pat. No. 4,624,937
comprises the step of treating the carbon catalyst to remove oxides from
the surface thereof.
Thus, it can be seen that processes for preparing quinoneimines from
hydroxydiphenylamines are known. Additionally, the use of various carbon
catalysts, including activated carbon, in chemical reactions is known.
However, in the conversion of hydroxydiphenylamine to an
N-phenyl-benzoquinoneimine, the use of a modified activated carbon
compound as an oxidation catalyst has not heretofore been suggested.
SUMMARY OF THE INVENTION
It has now been discovered that a hydroxydiphenylamine compound can be
converted into its corresponding N-phenyl-benzoquinoneimine by reacting
the hydroxydiphenylamine with oxygen or an oxygen containing gas in the
presence of a modified activated carbon catalyst.
The modified activated carbon catalyst of the present invention has been
treated to remove oxides from the surface thereof. Such a modified carbon
catalyst allows the conversion of hydroxydiphenylamine to the
corresponding N-phenyl-benzoquinoneimine in almost quantitative (HPLC)
yields.
In contrast to prior art, an advantage of using the process of the present
invention is that the conversion of hydroxydiphenylamine to the
corresponding N-phenyl-benzoquinoneimine is nearly quantitative. Thus,
very little waste material remains upon completion of the reaction.
Another advantage realized when using the modified activated carbon
catalyst set forth above is that the modified activated carbon catalyst
not only is recyclable, but it also avoids the drawbacks associated with
metal catalysts which include high cost, product contamination and
environmental waste concerns.
An additional advantage is that the modified activated carbon catalysts as
set forth herein provide a faster, more complete reaction compared to
commercially available activated carbon catalysts in the conversion of
hydroxydiphenylamines to N-phenyl-benzoquinoneimines.
Still further advantages of the present invention will become apparent to
those skilled in the art upon reading and understanding the following
detailed description of the preferred embodiments.
DETAILED DESCRIPTION OF THE INVENTION
The object of the present invention is to provide an effective process for
conversion of hydroxydiphenylamines to N-phenyl-benzoquinoneimines.
In accordance with the object of the invention, in a first embodiment, an
ortho- or para-hydroxydiphenylamine according to Formula I:
##STR1##
wherein R.sub.1 and R.sub.2 are independently selected from hydrogen,
hydroxyl, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, heterocycle, acyl,
aroyl, carbamyl, cyano, alkoxy, halogen, ether, thiol, amino, alkylamino,
and arylamino; is reacted in the presence of oxygen or an oxygen
containing gas and optionally, a solvent and heat, further in the presence
of a modified activated carbon catalyst which has had the surface oxides
removed therefrom.
The reaction produces a corresponding N-phenyl-benzoquinone-imine according
to Formula IIA or IIB:
##STR2##
The reaction is represented as follows:
##STR3##
Examples of satisfactory radicals for R.sub.1 and R.sub.2 are linear or
branched alkyls such as methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl, octyl, nonyl, decyl, dodecyl, and the like; aryls such as phenyl,
naphthyl, anthracyl, tolyl, ethylphenyl, and the like; cycloalkyls such as
cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like. Other
examples include allyl and isobutenyl; 1,3,5-sym-triazinyl,
2-benzothiazolyl, 2-benzimidazolyl, 2-benzoxazolyl, 2-pyridyl,
2-pyrimidinyl, 2,5-thiadiazolyl, 2-pyrazinyl, adipyl, glutaryl, succinyl,
malonyl, acetyl, acrylyl, methacrylyl, 3-mercaptopropionyl,
mercaptapyridazine, 2-mercaptobenzothiazole, caproyl, benzoyl, phthaloyl,
terephthaloyl, aminocarbonyl, carbethoxy, carbonyl, formyl, and the like.
These are merely exemplary radicals and are in no way intended to limit
the scope of the invention.
The modified activated carbon catalyst, described above, is prepared by
removing both acidic and basic surface oxides from the surfaces of a
carbon catalyst. A method for making the modified activated carbon
catalyst is set forth in U.S. Pat. No. 4,624,937.
According to U.S. Pat. No. 4,624,937, a carbon material, such as those
described in U.S. Pat. No. 4,264,776, is initially provided.
Ordinarily, the initial carbon catalyst used in preparing the modified
carbon catalyst is a commercially available activated carbon with a carbon
content ranging from about 10% for bone charcoal to about 98% for some
wood chars and nearly 100% for activated carbons derived from organic
polymers. The noncarbonaceous matter in commercially available carbon
materials will normally vary depending on such factors as precursor
origin, processing, and activation method. The treatment process can be
accomplished by a single or a multistep scheme which in either case
results in an overall chemical reduction of oxides on the carbon surface,
i.e., a reduction or removal of acidic oxides from the carbon surface.
As used herein, the term "oxides" is intended to mean carbon functional
groups which contain oxygen atoms as well as hetero-atom functional groups
which contain oxygen atoms. Other hetero-atom functional groups which do
not contain oxygen atoms may also be removed from the surface of the
carbon material during treatment.
In a two-step scheme, the carbon material can be first treated with an
oxidizing agent such as, for example, liquid nitric acid, nitrogen
dioxide, CrO.sub.3, air, oxygen, H.sub.2 O.sub.2, hypochlorite, or a
mixture of gases obtained by vaporizing nitric acid. The treatment can be
accomplished using either a gas or a liquid oxidizing agent. Where a
liquid is used, concentrated nitric acid containing from about 10 to about
80 g. HNO.sub.3 per 100 g. of aqueous solution is preferred. Preferred
gaseous oxidants include oxygen, nitrogen dioxide, and nitric acid vapors.
A particularly effective oxidant is nitric acid in the vapor phase which
includes nitric acid carried into the vapor phase by an entraining gas as
well as the vapors obtained by distilling liquid nitric acid. With a
liquid oxidant, temperatures from about 60.degree. C. to about 90.degree.
C. are appropriate, but with gaseous oxidants, it is often advantageous to
use temperatures of about 50.degree. C. to about 500.degree. C. or even
higher for the treatment step.
The treatment can be achieved by placing carbon from a manufacturer in a
round bottom flask which contains a magnetic stirring bar. Liquid nitric
acid is selected as the oxidizing agent for illustration. The amount of
carbon used is determined by the percent carbon load desired (% carbon
load %. of carbon used per 100 ml of nitric acid solution) and the nitric
acid solution volume to be used. Ordinarily, 1 to 200 g. of carbon per 100
ml of nitric acid or other liquid oxidizing agent is satisfactory.
Temperature control can be provided by any suitable means. A condenser and
scrubber can be connected to the round bottom flask as desired. A
calculated volume of water, preferably deionized water, is added to the
carbon, followed by sufficient (69-71%) nitric acid to achieve the desired
nitric acid solution. The carbon and nitric acid solution are then stirred
for the desired period at the desired temperature.
After stirring, the carbon is filtered, and the resulting wet cake may or
may not be washed and/or dried prior to pyrolysis.
The time during which the carbon is treated with the oxidant can vary
widely from about 5 minutes to about 10 hours. Preferably, a reaction time
of about 30 minutes to about 6 hours is satisfactory. When concentrated
nitric acid is the oxidant, a contact time of about 30 minutes to about 3
hours is satisfactory.
In a second step, the oxidized carbon material is pyrolyzed, i.e., heat
treated, at a temperature in the range of about 500.degree. C. to about
1500.degree. C., preferably from about 800.degree. C. to 1200.degree. C.
It is preferred to conduct the pyrolysis in an inert gas atmosphere, such
as nitrogen, argon, or helium.
Wet cake or dry carbon is placed in a ceramic pyrolysis dish which together
are placed in a quartz tube. Nitrogen is passed through water at about
70.degree. C., then through the quartz tube during pyrolysis. A dry,
static nitrogen atmosphere is maintained after flushing the quartz tube
with several tube volumes of dry nitrogen prior to pyrolysis. The quartz
tube containing the pyrolysis dish is placed in a suitable pyrolyzer
apparatus at about 930.degree. C. for the desired period, followed by
cooling while maintaining the nitrogen atmosphere.
Pyrolysis can last anywhere from about 5 minutes to 60 hours, although 10
minutes to 6 hours is normally satisfactory. The shorter times are
preferred for economic reasons because, as might be expected, continued
exposure of the carbon to elevated temperatures for prolonged periods can
result in a poor carbon catalyst for the oxidation. Pyrolysis may be
initiated in a slightly moist atmosphere or an atmosphere which contains
NH.sub.3 as this appears to produce a more active catalyst in a shorter
time.
Alternatively, the treatment is accomplished in a single step by pyrolyzing
the carbon material as described above while simultaneously passing a gas
stream comprised of NH.sub.3 and an oxygen-containing gas, e.g., H.sub.2
O/NH.sub.3, through the carbon. The flow rate of the gas stream should be
fast enough to achieve adequate contact between fresh gas reactants and
the carbon surface, yet slow enough to prevent excess carbon weight loss
and material waste. Many NH.sub.3 /oxygen-containing gas mixtures can be
used such as, for example, NH.sub.3 /CO.sub.2, NH.sub.3 /O.sub.2, NH.sub.3
/H.sub.2 O and NH.sub.3 /NOx, provided the gas mixture achieves the
desired result. Ordinarily, the oxygen-containing gas/NH.sub.3 ratio can
range from 0:100 to 90:10. Furthermore, nitrogen can be used as a diluent
to prevent severe weight loss of the carbon in high oxygen-containing gas
concentrations. Ammonia is a basic gas, and, as such, is believed to
assist the decomposition of the various oxide groups on the surface of the
carbon material. Any other chemical entity which will generate NH.sub.3
during pyrolysis should also prove satisfactory as an NH.sub.3 source. For
economic reasons, an NH.sub.3 /H.sub.2 O gas stream is most preferred.
The carbon materials treated according to the procedure set forth above,
when used in the catalytic oxidation of a hydroxydiphenylamine to the
corresponding N-phenyl-benzoquinoneimine, demonstrates a fast, efficient
conversion reaction without the drawbacks associated with using the heavy
metal catalysts of the prior art processes.
The catalyst loading concentration of the present invention is generally
about 0.5% to about 25.0% (wt/wt hydroxydiphenylamine). Preferably, about
10% (wt/wt hydroxydiphenylamine) catalyst is used in the reactions
according to the present invention.
Various solvents may be used in any of the reactions in accordance with the
present invention. Examples of solvents which may be used in the reactions
according to the present invention include, but are not limited to,
alcohols such as methanol, ethanol, isopropanol, methyl isobutyl carbinol,
ethylene glycol, etc.; ketones such as acetone and methyl isobutyl ketone,
cyclohexanone, 5-methyl-2-hexanone, 5-methyl-3-heptanone; aliphatic and/or
aromatic hydrocarbons such as alkanes, alkenes, toluene and xylene;
nitriles such as acetonitrile; halogenated solvents such as chloroform,
methylene chloride, and carbontetrachloride; and other solvents such as
N-methylpyrrolidone, THF, ethylacetate, dimethylformamide, and
dimethylsulfoxide, or any mixture of solvents would also be usable.
The starting material, a hydroxydiphenylamine (HDA), may be present at
concentrations from about 1.0% to about 75.0%.
The reaction may take place at varying temperatures in a range of from
about 0.degree. C. to about 100.degree. C. Preferably, the reaction
temperature is in a range of from about 20.degree. C. to about 80.degree.
C.
The reaction of the present invention takes place in an oxygen system.
Oxygen pressure can be varied with an effective range being between
atmospheric psig and 1500 psig. Preferably, the system is between 15 and
100 psig O.sub.2. The oxygen concentration can range from about 100%
O.sub.2 to about 2% O.sub.2 (using nitrogen or air dilution).
It is also possible to utilize a tertiary amine to accelerate the rate of
reaction in the process of the present invention. Tertiary amines usable
in the present invention include, but are not limited to, trialkyl- and
triaryl-amines. The addition of a tertiary amine will result in a basic pH
for the reaction. Preferably the pH is about pH8 to about pH9.
The present invention can be more clearly illustrated by the following
example(s). The modified activated carbon catalyst used in the examples
was prepared in accordance with the procedure set forth above.
EXAMPLE 1
A mixture of 5.0 g of 4-hydroxydiphenylamine (4-HDA), 0.5 g modified carbon
catalyst and 200 mL methanol was charged to an autoclave. The reaction
mixture was stirred and the autoclave, purged with oxygen, was then
charged to 30 psig of oxygen at 20-25.degree. C. The reaction mixture was
then heated to 50.degree. C. and maintained at 50.degree. C. until the
reaction was complete. As the reaction progressed, the oxygen pressure
dropped. When oxygen pressure dropped to about 20 psig, more oxygen was
charged to bring the pressure back to 30 psig. The reaction time was
counted from the moment oxygen was charged to the autoclave. The reaction
progress was monitored by analyzing samples using HPLC. When very little
or no oxygen uptake was detectable and the HPLC analysis indicated
disappearance of starting material 4-hydroxydiphenylamine, the product was
filtered to separate the catalyst. The reaction took about 1 hour and the
HPLC analysis of the mixture indicated 99.7 area % of the product
N-phenyl-p-benzoquinoneimine (NPQI). The product can be isolated in
greater than 90% yield. The product is brown solids with a melting point
of 100-103.degree. C.
Various isolation techniques well known in the art may be used to isolate
the product according to the present invention including, but not limited
to, crystallization, concentration and/or precipitation.
The catalyst and solvent recovered from the reaction can be recycled and
reused in subsequent reactions.
EXAMPLE 2
This example teaches the effect of using triethylamine to increase the rate
of reaction.
In accordance with procedure set forth in Example 1, a mixture of 5.0 g of
4-hydroxydiphenylamine (4-HDA), 0.5 g modified carbon catalyst, 1.5 g
triethylamine and 200 ml methanol was charged to an autoclave. The same
procedure as described in Example 1 was employed. The reaction took 20
minutes and the HPLC analysis of the mixture indicated 98.6 area % of the
product N-phenyl-p-benzoquinoneimine (NPQI).
Again, various isolation techniques well known in the art may be used to
isolate the product according to the present invention including, but not
limited to, crystallization, concentration and/or precipitation.
The catalyst and solvent recovered from the reaction can be recycled and
reused in subsequent reactions.
EXAMPLE 3
In accordance with procedure set forth in Example 1, 5.0 g of
4-hydroxydiphenylamine (4-HDA) in 200 mL toluene and 0.5 g modified carbon
catalyst were charged to an autoclave. The same procedure as described in
Example 1 was employed. The reaction was carried out to completion in less
than 1.25 hrs and the catalyst was separated from the product by simple
filtration. HPLC analysis of the mixture indicated greater than 95 area %
of the product N-phenyl-p-benzoquinoneimine.
A comparison of the following two examples clearly indicate the advantages
of triethylamine on the rate of reaction.
EXAMPLE 4
A mixture of 5.0 g of 4-hydroxydiphenylamine (4-HDA), 0.5 g modified carbon
catalyst and 200 mL methanol was charged to an autoclave. The reaction
mixture was stirred and the autoclave, purged with oxygen, was then
charged to 30 psig of oxygen at 21.degree. C. The reaction mixture is was
then maintained at 21.degree. C. until the reaction was complete. As the
reaction progressed, the oxygen pressure dropped. When oxygen pressure
dropped to 20 psig, more oxygen was charged to bring the pressure back to
30 psig. The reaction time was counted from the moment oxygen was charged
to the autoclave. The reaction progress was monitored by analyzing samples
using HPLC. The following table summarizes the results
TABLE 1
Sample No. Time (minutes) Area % 4-HDA Area % NPQI
1 10 31.1 68.2
2 20 30.1 69.3
3 30 14.9 83.1
4 40 13.8 85.6
5 50 8.15 90.4
6 60 7.5 90.9
7 70 5.4 94.2
8 80 3.6 96.1
9 90 3.3 94.6
10 100 1.6 97.5
11 110 0.85 98.6
When very little or no oxygen uptake was detectable and the HPLC analysis
indicated disappearance of starting material 4-hydroxydiphenylamine, the
product was filtered to separate the catalyst. The HPLC analysis of the
mixture indicated 98.6 area % of the product N-phenyl-p-benzoquinoneimine
(NPQI).
Again, various isolation techniques well known in the art may be used to
isolate the product according to the present invention including, but not
limited to, crystallization, concentration and/or precipitation.
The catalyst and solvent recovered from the reaction can be recycled and
reused in subsequent reactions.
EXAMPLE 5
In accordance with procedure set forth in Example 4, a mixture of 5.0 g of
4-hydroxydiphenylamine (4-HDA), 0.5 g modified carbon catalyst, 200 mL
methanol and 1.5 g triethylamine was charged to an autoclave. The reaction
mixture was stirred and the autoclave, purged with oxygen, was then
charged to 30 psig of oxygen at 21.degree. C. The reaction mixture was
then maintained at 21.degree. C. until the reaction was complete. As the
reaction progressed, the oxygen pressure dropped. When oxygen pressure
dropped to 20 psig, more oxygen was charged to bring the pressure back to
30 psig. The reaction time was counted from the moment oxygen was charged
to the autoclave. The reaction progress was monitored by analyzing samples
using HPLC. The following table summarizes the results:
TABLE 2
Sample No. Time (minutes) Area % 4-HDA Area % NPQI
1 10 18.3 80.5
2 20 8.7 90.5
3 30 3.7 93.9
4 40 2.1 96.9
5 50 1.3 98.3
6 60 0.77 99.2
When very little or no oxygen uptake was detectable and the HPLC analysis
indicated disappearance of starting material 4-hydroxydiphenylamine, the
product was filtered to separate the catalyst. The HPLC analysis of the
mixture indicated 99.2 area % of the product N-phenyl-p-benzoquinoneimine
(NPQI).
This clearly indicates that the rate of reaction in the presence of
triethylamine is extremely faster in comparison to the one without it.
The N-phenyl-benzoquinoneimines of the present invention may be used as
starting materials in the production of aminodiphenylamines.
Para-aminodiphenylamines are used in the production of numerous rubber
chemicals including antidegradants, gel inhibitors and polymerization
inhibitors. Further, the N-phenyl-benzoquinoneimines also exhibit
performance enhancement properties when used as rubber additives.
The invention has been described with reference to the preferred
embodiments. Obviously, modifications and alterations will occur to others
upon reading and understanding the preceding detailed description. It is
intended that the invention be construed as including all such
modifications and alterations in so far as they come within the scope of
the appended claims or the equivalents thereof.
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